Polycarboxy acid esters of oxypropylated sulfone amides



United States Patent POLYCARBOXY ACID ESTERS (9F OXYPRG- PYLATED SULFGNEAMIDES Melvin De Groote, St. Louis, Mo., assignor to PetroliteCorporation, a corporation of Delaware No Drawing. Original applicationDecember 1, 1950, Serial No. 198,751, now Patent No. 2,626,902, datedJanuary 27, 1953. Divided and this application December 2, 1952, SerialNo. 323,727

Claims. '(Cl. 260-475) The present invention is concerned with certainnew chemical products, compounds or compositions which have usefulapplication in various arts.

The particular compounds subsequently described herein in greater detailare hydrophile synthetic products, and more particularly, fractionalesters obtained from a polycarboxy acid and a diol containing bothnitrogen and sulfur obtained by the oxypropylation of a sulfonamidehaving not more than 7 uninterrupted carbon atoms in any single radicaland containing a phenyl radical. For all practical purposes this limitsthe sulfonamide to benzene sulfonamide, toluene sulfonamide, andsulfonic amides obtained from anisole, phenetole, or sulfonamidesobtained from comparable ethers in which the alkyl group contains morethan 3 carbon atoms but not over 7 carbon atoms, and containing thephenyl radical. Furthermore, the dihydroxylated compound prior toesterification must be water-insoluble and kerosene-soluble. Momentarilyignoring certain variants of structure which will be consideredsubsequently, the products of the present invention may be' exemplifiedby the following formula:

inwhich R is a member of the class of aromatic'hydrocarbon radicals andoxygen-interrupted aromatic hydrocarbon radicals having a single etherlinkage, with the proviso that the entire class be free from any radicalhaving more than 7 uninterrupted carbon atoms in a single group; and nand n are whole numbers with the proviso that n plus n equals a sumvarying from to 80; n" is a whole number not over 2 and R is the radicalof the polycarboxy acid preferably free from any radicals having morethan 8 uninterrupted carbon atoms in a single group, and with thefurther proviso that the parent dihydroxy compound prior toesterification be water-insoluble and kerosenesoluble.

The products of this invention have particularvalue as demulsifyingagents in a process for resolving petroleurn emulsions of thewater-in-oil type that are commonly referred to as cut oil, roily oil,emulsified oil, etc., and which comprise fine droplets ofnaturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion. A process for resolving petroleum emulsions ofthe water-in-oil type which utilizes the products described herein isdescribed and claimed in my copending application Serial No. 198,751,filed December 1, l950 now Patent 2,626,902, granted January 27, 1953.

2,743,292 Patented Apr. 24, 1956 ing emulsions, as spreaders in theapplication of asphalt in road building and the like, asflotationreagents, as

lubricants, etc.

As previously stated one preferably uses benzene sul fonamide or toluenesulfonamide. I have-used either one or both of these amides andalsoafter treatment with l, 2, 3 01'4 moles of ethylene oxide.) If there isany choice I prefer to use benzene sulfonamide or -oxyethylated benzenesulfonamide'particularly an oxyethylated benzene sulfonamide which hasbeen treated with either one mole or two moles of ethylene oxide.

Obviously a suitable sulfonamide such as benzene sulfonamide or toluenesulfonamide could be treated with compounds which would yield aderivative having both a hydroxyl radical and a side chain ether radicalas, for example, reactions involving benzenesulfonamide on the one handand allyl glycidyl-ether,- glycidyl isopropyl ether, glycidyl phenylether, or the like, on the other hand. Such compounds, of course, couldstill be treated with a mole or more of ethylene oxide before reactingwith propylene oxide to produce the oxypropylated deriva-' tivesdescribed subsequently in greater detail.

What has been said previously in regard to the mate-' rials hereindescribed and particularly for use 'as demulsifiers with reference tofractional esters, may be and probably is an oversimplification forreasons which are obvious on further examination. The assumption hasbeen and it is believed to be largely true that'the' oxypropylation of asulfonamide produces'a dihydroxylated compound. There is someevidencebased on abnormal molecular weights that at least in part undercertain conditions one does not necessarily obtain a hundred per centdihydroxylated compound but onemay obtain a monohydroxylated compounddue to the fact only one amido hydrogen is attacked by the alkyleneoxide and this would be true whether it happened to be propylene oxideor some other oxide, such as ethylene oxide.

If this is the case it is purely a matter of speculation at the momentbecause apparently there is no data which determines the mattercompletely under all conditions of manufacture and one has a situationsomewhat comparable to the acylation of monoethanolamine ordiethanolamine, i. e., acylation can take place involving either thehydrogen atom attached to oxygen or the hydrogen atom attached tonitrogen.

However, as far as the herein described compounds are concerned it wouldbe absolutely immaterial except that one would have in part a compoundwhich might be a fractional ester and might also have an amide structurewith only one carboxylradical of the polycarboxylated reactant involved.It would be comparable to obtaining a oxypropylation followed byoxyethylation.

propylation products obtained from the specified sulfon- V amides; and

Part 4 is concerned with certain derivatives whichv can be obtained fromthe oxypropylated sulfonamides. In some instances, such derivatives areobtained by modest oxyethylation preceding the oxypropylation step, orThis results in diols having somewhat difierent properties which canthen be reacted with the same polycarboxy acids or anhydrides describedin Part 2. For this reason a description of the apparatus makes casualmention 'of oxyethylation. For the same reason there is brief mention ofthe use of glycide.

'- PART 1 c 4 Example 2a Approximately 40.7'poi1nds of the reaction massidentified as Example 1a, preceding, were permitted to remain For anumber of 'well-known reasons equipment,

whether laboratory size, semi-pilot plant size, pilot plant size, orlarge-scale size, is not as a rule designed for a particular alkyleneoxide. lnvariably and inevitably, however, or particularly in the caseof laboratory equipment and pilot plant size the design is such as touse any of the customarily available alkylene oxides, i. e., ethyleneoxide, propylene oxide, butylene oxide, glycide, epichlorohydrin,styrene oxide, etc. In the subsequent description of the equipment itbecomes obvious that it. is adapted for oxyethylation as well asoxypropylation.

The procedures used for the oxypropylation operation are substantiallythe same as those conventionally used in carrying out oxypropylations,and for this reason, the oxypropylation step will simply be illustratedby the following specific examples.

' Example 1a The starting material was a commercial grade of henzene'sulfonarnide. The particular autoclave employed was one with a capacityof gallons or on the average of about 120 pounds of reaction mass. Thespeed of the stirrer could be varied from 150 to 350 R. P. M.Approximately 7.12 pounds of benzene sulfonamide were charged into theautoclave alongwith .75 pound of canstic soda. The reaction pot wasflushed out with'nitrogen. The autoclave was sealed and the automaticdevices adjusted and set for injecting a total of 56.25 pounds ofpropylene oxide in slightly less than a 4-hour period. The pressureregulator was set for a maximum of pounds per square'inch. This meantthat the bulk of the reaction could take place, and probably did takeplace, at a lower pressure. This comparatively low pressure was theresult of the fact that considerable catalyst was present. The propyleneoxide was added comparatively slowlyand more important the selected.temperature range was 220 to 225 F. (slightly higher than the boilingpoint of water). The initial introduction of propylene oxide was notstarted until the heating devices had'raise'd the temperature to aboutthe boiling-point of water. At the completion of the reaction a samplewas taken and oxypropylation proceeded as in Example 2a following. 7

in'the reaction vessel and 'withoutthe addition of any more catalyst22.62 pounds of propylene oxide were added. The oxypropylation wasconducted in substantially the same manner with regard to pressure andtempera- 5 ture as in Example 1a, preceding, except'that the'reactionperiod was complete in less time, i. e., 1 /2 hours instead of 3 /2hours. At the end of the reaction period part of the reaction mass waswithdrawn and employed as a sample and oxypropylation was continued withthe. remainder of the reaction mass as describedin Example 44.3 poundsof the reaction mass identified as Example 2a, preceding, were permittedto remain in the reaction vessel. 23.25 pounds ofp'ropylene oxide wereintroduced in this third-stage. No additional catalyst was added. Thetime period required was slightly more than in Example Za, preceding, towit, two hours. The conditions of reaction as far as temperature andpressure were concerned. were substantially the same as in' Example 1a,

preceding. 5

At the completion of the reaction part of the reaction mass waswithdrawn and the remainder subjected to oxypropylation as described inExample 4a, following.

Example 4a 49.8 pounds of the reaction mass identified as Example 35,preceding, were permitted'to remain in the autoclave. Without adding anymore catalyst this mass was subjected'to' further oxypropylation as 'inthe preceding examples. The amount of propylene oxide added was slightlyless than 27.75 pounds. This was introduced in a 4-hour period.Conditions in regard to temperature and pressure were substantially thesame. as in Example 1a, preceding. At the end of the reaction periodpart of the sample was withdrawn and the remainder of the reaction masswas subjected to further oxypropylation as described in Example 5a,following.

Eicdmple'Sa Approximately 49 pounds of the reaction mass were.

permitted to stay in the autoclave. No additional catalystwasintroduced.17.25. pounds ofpropylene oxide were added. The time requiredto add thispropylene oxide was 5 /2 hours. The conditions of reaction in regard totemperature and pressure were substantially the same as inExample 1a,p'receding 5 V In this particular series of examples the oxyprop ylationwas stopped at this stage. In other-series I' have continued theoxypropylation so that the theoretical molecular weight varied tosomewhat short of 10,000 but the increase in molecular weightby hydroxyldetermination was comparatively small, i. e.,' just slightly past 3,000.

Incidentally, the above examples were repeated using toluene sulfonamideand for all practical purposes the resultsobta ined were almostidentical at each point.

What is said herein is'presented intabular form in. Table 1 immediatelyfollowing, with some added information as'to molecular weight and as tosolubility of the reaction product in water, xylene, and kerosene.

TABLE '1' Composition before Composition at end V N Max Ex. by hyd pres111110, No. Amide Oxide Theo Amide Oxide V deteri lbs amt., amt., ig11:01., amt., amt., iig min sq 11 lbs. lbs. 1 Wt. 155., lbs.

1a- 7. 12 .75 1 395 7. 12 55. 25 1, 530 220-225 25-37 4 2a. 4. 52 35. 7347 2,135 4. 52 5s. 35 47 1, 525 220-225 35-37 5 8a.. a. 15 40. 83 33 2,335 3. 10 64. 0s 33 2, 510 220-225 35-37 2 4a. 2. 33 47. 1s 27 5, 495 2.5a 74. 93 27 2, 440 220-225 5-37 4 5a 1.48 47. 53 17 7,015 1.48 04.78 172. 000 220-225 35-37 5 /2 v Example 1a was emulsifiable to insoluble inwater, but soluble in xylene and insoluble in kerosene. Example 2a wasinsoluble in water, soluble in xylene, and insoluble in kerosene.Examples 3a, 4a and 5a were all insoluble in water, soluble in xyleneand soluble in kerosene. This was true also of other examples in whichthe theoretical molecular weight was somewhat higher than the maximumtheoretical range indicated above, i. e., a theoretical range of 8,000to 10,000.

' This applied also to samples obtained in substantially the s amemanner from toluene sulfonchloride. The final product at the end of theoxypropylation step was a somewhat viscous fluid with a slightly reddishtinge. This is characteristic of all the products obtained at thevarious stages above noted. The products were, of course, slightlyalkaline due to the residual caustic soda. The residual basicity due tothe catalyst would, of course, be the same if sodium methylate had beenused.

,Speaking of insolubility in water or solubility in kerosene suchsolubility test can be made simply by shaking small amounts of thematerials in a test tube with water, for instance, using 1% to 5%approximately based on the amount of water present.

Needless. to say, there is nocomplete conversion of propylene oxide intothe desired hydroxylated compounds. This is indicated by the fact thatthe theoretical molecular weight based on a statistical average isgreater than the molecular weight calculated by usual methods on basisof acetyl or hydroxyl value. Actually, there is no completelysatisfactory method for determining molecular weights of these types ofcompounds with a high degree oiaccuracy when the molecular weightsexceed 2,000. In some instances the acetyl value or hydroxyl valueserves as satisfactorily as anindex to the molecular weight as any otherprocedure, subject to the above limitations, and especially in thehigher molecular weight range. If any difficulty is encountered in themanufacture of the esters as described in Part 2 the stoichiometricalamount of acid or acid compound should be taken which corresponds to theindicated acetyl or hydroxyl value. This matter has been discussed inthe literature and is a matter of common knowledge and requires nofurther elaboration.

PART 2 As previously pointed out the present invention is concerned withacidic esters obtained from the oxypropylated derivatives described inPart 1, immediately pre ceding, and polycarboxy acids, particularlydicarboxy acids such as adipic acid, phthalic acid or anhydride,succinic acid, diglycollic acid, sebacic acid, azelaic acid, acom'ticacid, maleic acid or anhydride, citraconic acid or anhydride, maleicacid or anhydride adducts as obtained by the Diels-Alder reaction fromreactants such asmaleic anhydride 'and cyclopentadiene. Such acidsshould be heat stable so they are not decomposed during esterification.They may contain as many as 36 carbon atomsas, for example, the acidsobtained by dimerization of unsaturated fatty acids, unsaturatedmonocarboxy fatty acids, or unsaturated monocarboxy acids having 18carbon atoms. Reference to the acid in the hereto appended claimsobviously includes the anhydrides or any other obvious equivalents. Mypreference, however, is to use polycarboxy acids having not over 8carbon atoms.

The production of esters including acid esters (fractional esters) frompolycarboxy acids and glycols or other hydroxylated compounds is wellknown. Needless to say, various compounds may be used such as the lowmolal ester, the anhydride, the acyl chloride, etc. However, for purposeof economy it is customary to use either the acid or the anhydride. Aconventional procedure is employed. On a laboratory scale one can employa resin pot of the kind described in U. S. Patent No. 2,499,370, datedMarch 7, 1950, to De Groote & Keiser, particularly with one more openingto permit the use of a porous spreader if hydrochloric acid gas is to beused as a catalyst.

Such device or absorptidri 'spr'eader cons istsof minute Alundumthimbles which are connected to a glass tube. One can add a sulfonicacid such as paratoluene sulfonic acid as a catalyst. There is someobjection to this because in some instances there issome evidence thatthis acid catalyst tends to decompose or rearrange available of removingthe paratoluene sulfonic acid or.

If hydrochloric acid, is.

other sulfonic acid employed. employed one need only pass the gasthrough atran exceedingly slow rate so as to keep the reaction massacidic Only a trace of acid need be present. I have employedhydrochloric acid gas or the aqueous acid itself to eliminate theinitial basic material. My preference, however, is to use no catalystwhatsoever and to insure complete dryness of the diol as described inthe final procedure just preceding Table 2.

The products obtained in Part 1 preceding may contain a basic catalyst.As a general procedure I have added an amount of half-concentratedhydrochloric acid. considerably in excess of what is required toneutralize the residual catalyst. The mixture is shaken thoroughly andallowed to stand overnight. It is thenfiltcrcd and refluxed with theXylene present until the water can be separated in a phase-separatingtrap. As soon as the product is substantially free from water thedistillation stops. This preliminary step can be carried out in theflask to be used for esterification. If there is any further depositionof sodium chloride during the reflux stage needless to say a secondfiltration may be required. In any event the neutral or slightly acidicsolution of the oxypropylated derivatives described in Part 1 is thendiluted further with sufficient xylene, decalin, petroleum solvent, orthe like, so that one has obtained approximately a 45% solution. To thissolution there is added a polycarboxylated reactant as previouslydescribed, such as phthalic anhydride, succinic acid or anhydride,diglycollic acid, etc. The mixture is refluxed until esterification iscomplete as indicated by elimination of water or drop in carboxyl value.Needless to say, if one produces a half-ester from an anhydride such asphthalic anhydride, no Water is eliminated. However, if it is obtainedfrom diglycollic acid, for example, 'water is eliminated. All suchprocedures are conventional and have been so thoroughly described in theliterature that further consideration will be limited to a few examplesand a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any,can be employed. For example, the oxyalkylation can be conducted inabsence of a solvent or the solvent removed after oxypropylation. Suchoxypropylation end product can then be acidified with just enoughconcentrated hydrochloric acid to just neutralize the residual basiccatalyst. To this product one can then add a small amount of anhydroussodium sulfate (sufiicient in quantity to take up any water that ispresent) and then subject the mass to centrifugal force so as toeliminate the hydrated sodium sulfate and probably the sodium chlorideformed. The clear somewhat viscous strawcolored amber liquid so obtainedmay contain a small amount of sodium sulfate or sodium chloride but, inany event, is perfectly acceptable for esterification in the mannerdescribed.

It is to be pointed out that the products here described are notpolyesters in the sense that there is a plurality of both diol radicalsand acid radicals; the product is characterized by having only one diolradical.

In some instances and, in fact, in many instances I have found that inspite of the dehydration methods employed above that a mere trace ofwater still comes through and 7 that this mere trace of water certainlyinterferes with the acetyl or hydroxyl value determination, at leastwhen a number of conventional procedures are used and may retard'estenfication, particularly where there is no 8111 fonic acid orhydrochloric acid present as a catalyst. Therefore, I have preferred touse the following procedure: I have employed about 200 grams of the diolas described in Part 1, preceding; I have added about 60 grams ofbenzene, and then refluxed this mixture in the glass resin pot using aphase-separating trap 5551015 benzene carried out all the water presentas water of solution or the equivalent. Ordinarily this refluxing Thesesolvents sequently except by vacuum distillation and provided there. isno objection to a little residue. Actually, when thesematerials are usedfor a purpose such as demulsification the solvent might just as well beallowed toremain. If f I the solvent is to be removed by distillation,and partic-- ularly vacuum distillation, then the high boiling aromaticpetroleum solvent might well be replaced by some more expensive solvent,such'as decalin or an alkylated decalin whichhas a rather'definiteorclose rangeboiling point.

10 The removal of the solvent, of course, is purely a conventionalprocedure and requires no elaboration.

In the appended table solvent #73,,which appears in all instances, is amixture of 7 volumes of thearomatic petroleum solvent previouslydescribed and 3 volumes of a benzene.

This was used, or a' similar mixture, in the manner previouslydescribed.

to use the petroleum solvent-benzene mixture although obviously any ofthe other mixtures, such as decalin and In a large number of Sim; ilarexamples decalin has been used but it is my preference to use theabove-mentionedmixture and particularly with the preliminary, step ofremoving all the water. If one 20 does not intend to remove the solventmy preference is I have employed and found very satisfactory is thefollowing: V 2

I. B. P., 142 C. ml., 200 C.

V xylene, canbe employed' Y 5 o The dataincluded in the subsequenttables, i. e., Tables 50 242 5 2 and 3, are self-explanatory, and verycomplete and it is 55 ml., 244 c. 25

60 248 C. believed no further elaboration s necessary:

Amt. of Amt. of Ex. No. of Theo. hy- Actual M01. wt. Ex. No. of Theo. M.W. hyd. polycaracid ester oxy. OI H C droxsl V. hydroxyl based on compd.Polycarboxy reactant boxy react V cmpd. of H. 0 value actual H. N. (gm)7 ant g 7 1b 1a 1, 395 80. 4 84. 5 1, 330 204 Diglyeollic'acid 41. 3 251a 1, 395 80. 4- 84. 5 1, 330 210 Phthalic anhyd 45. 7 3b 1a 1, 395 80.4 84. 5 1. 330 203 Maleie anhyd 30. 0 4b 1, 395 80. 4 84. 5 1, 330 20152. 5 5b 10 1,395 80. 4 34. 5 1,830 202 34.0 55 2,185 5 51.5 73.4 1,525201 35.4 '75 2a 2, 185 51. 5 73. 4 1, 525 205 40. 0 8b 211 2,185 51.573.4 1,525 207 25.4 95 2a 2, 185 51. 5 73. 4 1, 525 208 47. 4 10b 20 2,185 51. 5 73. 4 1,525 208 30. 5 11!; 3a 3, 335 33. 5 48. 4 2, 310 20724. 0 12b 3, 335 33. 5 48. 4 2, 310 208 25. 7 130 3a 3, 335 V 33. 5 48.4 2, 310 207 17. 5 140 32 3,335 33.5 48.4 2,310 207 31.1 15!) 30 3,33533.5' 48.4 2,310 205 20.0 160 3a 3, 335 33. 5 48. 4 2, 310 208 22. 4 17b45 5, 495 17. 3 45 2, 440 205 22.4 180 4a 5, 495 17. 3 45 0 208 25. 219b 5,495 17.3 2,440 208 15. 200 45 5,495 17.3 .45 2,440 207 29.5 210 4a5, 495 17.3 45 2, 440 V 207 19. 0 22b 45 5, 495 17.3 45 2, 440' 200 21.5 23b 52 7, 015 15. 0 43. 2 2, 500 205 21. 2 245 7,015 15.0 43 2 2,500205 23.5 250 v 50 7,015 16.0 43 2 2, 600 206 Maleic anhyd. 15.5 255 527,015 15.0 43 2 2, 500, 205 Aconitic 551m; 27.3 27b 50 7,015 16.0 43 22,600 208 Citraconic anhyd- 17.9 280 50 7,015 7 --15.0 43 2 2,500 205015115 acid a 19.9

TABLE 3 Esterifica- Time otes- V 55V Ex .No.of Amt. 501-, Water out 15ml., 215 0. 55 ml., 252 c. amdester smut y fls 3.2%??- ififig? 55. 20ml., 216 ml., 252 C. 240 M9 7 25 ml., 220 0. ml., 250 0. .3, 257 5 3 Q30 ml., 225 C. ml., 264 C. gig-g fig 1 None 35 m1.,230 c. ml., 270 c. 7.153 40 ml., 234 C. ml., 280 C. #7-3 231 155 2 a 4.9 1 a e #7-3 2 1 45ml., 237 c. ml., 307 0. W3 $2 132 5f; {#33: #7-3' 250 158 4 49 Afterthis material is added, refluxmg is continued, and, #73 238 153 2% 7None of course, is at a high temperature, to wit, about 160 it; V 5 g-ito 170 C If the carboxy reactant is an anhydride need- #73 2 25 155 3 2less to say no water of reaction appears; if the carboxy it; 323 g greactant is an acid water of reaction should appear and #7-3 220 151 1%10.3 should be eliminated at the above reaction temperature. it? 3 If itis not eliminated I simply separate out another 10 #7-3 225 158, 2 Noneto 20 cc. of benzene by means of the phase-separating 33% 5g 3 trap andthus raise the temperature to 180 or 190 C., #7-3 210 10.5 even to 200C., if need be. My preference is not to go 3-2 above 200C. .7 #73 222 3%N555 The use of such solvent is extremely satisfactory pro i513 f videdone does not attempt to remove the solvent sub #7-3 217 2% 8.8

The procedure for manufacturing the esters has been illustrated bypreceding examples. If for any reason reaction does not take place in amanner that is acceptable, attention should be directed to the followingdetails: (a) Recheck the hydroxyl or acetyl value of the oxypropylatedproducts of the kind specified and use a stoichiometricallyequivalent'amount of acid; (b) if the reaction does not proceed withreasonable speed either raise the temperature indicated or else extendthe period of time up to 12 or 16 hours if need be; (c) if necessary,use /2% of paratoluene sulfonic acid or some other acid as a catalyst;(d) if the esterification does not produce a clear product a checkshould be made to see if an inorganic salt such as sodium chloride orsodium sulfate is not precipitating out. Such salt should be eliminated,at least for exploration experimentation, and can be removed byfiltering. Everything else being equal as the size of the moleculeincreases the reactive hydroxyl radical represents a smaller fractionof. the entire molecule and thus more .difiiculty. is involved-inobtaining complete es'terification.

Even under the most carefully controlled conditions of oxypropylationinvolving comparatively low temperatures and long time of reactionthereare formed certain compounds whose compositions arestill obscure.Such side reaction products. can contribute a substantial proportion ofthe final cogeneric reaction mixture. Various suggestions have been madeas to the nature of these compounds, such as being cyclic polymers ofpropylene oxide, dehydration products with the appearance of a vinylradical, or isomers of propylene oxide or derivatives thereof, i. e., ofan aldehyde, ketone, or allyl alcohol. In some instances an attempt toreact the stoichiometric amount of a polycarboxy acid with theoxypropylated derivative results in an excess of the carboxylatedreactant for the reason that apparently under conditions of reactionless reactive hydroxyl radicals are present than indicated by thehydroxyl value. Under such circumstances there is simply a residue ofthe carboxylic reactant which can be removed by filtration or, ifdesired, the esterification procedure can be repeated using anappropriately reduced ratio of carboxylic reactant.

Even the determination of the hydroxyl value by conventional procedureleaves much to be desired due either to the cogeneric materialspreviously referred to, or for that matter, the presence of anyinorganic salts or propylene oxide. Obviously this oxide should-beeliminated.

The solvent employed, if any, can be removed from the finished ester bydistillation and particularly vacuum distillaiton. The final products orliquids are gen erally pale reddish amber to reddish amber in color, andshow moderate viscosity. 7 They can be bleached with bleaching clays,filtering chars, and the like. However, for the purpose ofdemulsification or the like color is not a factor and decolorization isnot justified.

In the above instances I have permitted the solvents to remain presentin the final reaction mass. In other instances I have followed the sameprocedure using decalin or a mixture of decalin or benzene in the samemanner and ultimately removed all the solvents by vacuum distillation.Appearances of the final products are much the same as the diols beforeesterification and in some instances were somewhat darker in color andhad a more reddish cast and perhaps somewhat more viscous.

PART 3 Previous reference has been made to the fact that diols(nitrogen-free compounds) such as polypropylene glycol of approximately2,000 molecular weight, for example, have been esterified with dicarboxyacids and employed as demulsifying agents. The herein describedcompounds are different from such diols although both, it is true, arehigh molecular weight dihydroxylated compounds.

group. Furthermore, there is present a benzene ring. In any event, acombination of nitrogen, sulfur and a benzene ring introducesrentirelydifferent characteristics than appear in ordinary polypropylene glycolof acornparable molecular Weight. It seems reasonable to as sume thatthe orientation of such molecules are affected by the presence of suchparticular structure insofar that presumably it would lead toassociation by hydrogen,

bonding or some other eflect.

Regardless of what the difference may be the fact." still remains thatthe compounds of the kind herein de-' scribed may be, and frequentlyare,10%, 15% or 20%.,

better on a quantitative basis than the simpler compound previouslydescribed, and demulsify, faster and. give cleaner oil in manyinstances. comparative tests hasbeen describedbin a booklet entitledTreating Oil Field Emulsions,..lused in .the..Vo.- cational TrainingCourse, Petroleum Industry. Series,,of

theAmerican Petroleum Institute.

It may be well to emphasize also the fact that city-- propylation doesnot produce a single compound but a cogeneric mixture. The factorinvolved is the same as appears if one were oxypropylating amonohydricalcohol or a glycol. Momentarily, one may consider thestructure of a polypropylene glycol, such'as polypropylene glycol of2000 molecular weight. Propylene glycol has a primary alcohol radicaland a secondary alcohol In this sense the building unit which formsradical. polypropylene glycols is not symmetrical. Obviously,

then, polypropylene glycols canbe obtained, at; least v theoretically,in which two-secondary alcohol groups are united or asecondary-alcoholgroup is united -to'a--pri-' mary alcohol group,etherization being involved, of course, in each instance. 7

Usually no effort is made to-ditferentiate between oxy-' propylationtaking place,-for-example, at the primary" alcohol -unit radical-or the,secondary alcohol radical. Actually, when such products areobtained,1such as a high molal polypropyleneglycol or theproducts-obtained. in themanner herein described one does not obtain'a'bers of the mixture. On a statistical basis, of'course, n can beappropriately specified. This means that -from' the practicalstandpoint, i. e., the ability to describe how to make the product underconsideration and how to repeat such production time after-time withdifliculty, it is necessary to resort to some other method ofdescription, or else consider the value of n, in formulas such as thosewhich have appeared previouslyand which appeat such production timeafter time without difiiculty, it

stituents in which n has a single definite-value, and also with theunderstanding that n represents the average statistical value based onthe assumption of completeness of reaction.

This may be illustrated asfollows: Assume that in any particular examplethe molal ratio of the propylene oxide to benzene sulfonamide or otherspecified aromatic sulfonamide is 30 to 1. Actually, one obtainsproducts in which n probably varies from 10 to 20, perhaps even further.The average value, however, is 15, assuming, as previously stated, thatthe reaction is complete; The product described by the formula is bestdescribed also in terms of method of manufacture.

PART 4 The instant compounds hav e present a nitrogen atom and also asulfur atom as part of a sulfonar'nide' The method. of.,rnaking such.

Rather, one obtains a cogeneric mixture of.

V '11 ing agents other than propylene oxide, such as ethylene oxide.Obviously variants can be prepared which do not depart from'what is saidherein but 'do produce modifications. Benzene sulfonamide or othersuitable aromatic sulfonamide can be reacted with ethylene oxide inmodest amounts and then subjected to oxypropylation provided that theresultant derivative is (a) water-insoluble, (b) kerosene-soluble, and(c) has present to 80 alkylene oxide radicals. Needless to say, in orderto have waterinsolubility and kerosene-solubility the large majoritymust be propylene oxide. Other variants suggest themselves as, forexample, replacing propylene oxide .by butylene oxide. V

More specifically, one mole of benzene sulfonamide can be treated with2,4 or 6 moles of ethylene oxide and then treated with propylene oxideso as to produce a water-insoluble, kerosene soluble oxyalkylatedproduct in which there are present 15 to 80 oxide radicals aspreviouslyspecified. Similarly the propylene oxide can be added firstand then the ethylene oxide, or random oxyalkylation can be employedusing a mixture of the two oxides. The compounds so obtained are readilyesterified be introduced also by means of a sulfating agent as'previously suggested, or by treating the chloroacetic acid resultantwith sodium sulfite. I a

I have found that if such hydroxylated compound or compounds are reactedfurther so 'as to produce entirely new derivatives, such new derivativeshave the properties of the original hydroxylated compound insofar thatthey are efiective and valuable de'mulsifying agents for resolution ofwater-in-oil emulsions as found in the petroleum industry, as breakinducers in doctor treatment of' sour crude, etc.

This applicationis a division of my copending appli cation Serial No.198,751, filed December 1, "1950, now Patent 2,626,902, granted January27, 1953.

more than 8 carbon atoms and selected from the group.

from the class consisting 7 RI i V V in which R is a memberof the classof rnonoc'yclic aromatic hydrocarbon radicals and oxygen-interruptedmonocyclic aromatic hydrocarbon-radicals having a single ether linkage,with the'proviso that the entire class be free from any radical havingmore than 7 uninterrupted carbon atoms in a single group; and n and nare whole numbers with the proviso that 1 plus n .equals'a sum varyingfrom 15 to 80; n is awhole number not over 2 and R is the'radical of' apolycarboxy acid'having not consisting of acyclic and isocyclicpolycarboxy acids composed of carbon, hydrogen and oxygen of the formulaOOOH and with the further proviso that the parent dihydroxy compoundprior to esterification be water-insoluble and kerosene-soluble.

Having-thus described my, invention whatI claim as new and desire tosecure by Letters Patent, is:

1. Hydrophile synthetic products; said'hydrophile synthetic productsbeing a cogeneric mixture selected from the class consisting of acidicfractional esters and acidic amido derivatives obtained by'reactionbetween (A) a polycarboxy acid of the structure C O OH in which R is,the radical of a polycarboxy acid having' not more than 8 carbonatoms'and selected from the 7 class consisting of acylic and isocyclicpolycarboxy acids 'in which R' is a member of the class of monocyclicaromatic hydrocarbon radicals and oxygen-interrupted monocyclicaromatic'hydrocarbon radicals having a single ether linkage, with theproviso that the entire class be free from any radical having more than7 uninterrupted carbon atoms in a single group; and R" is selected 3.Hydrophile synthetic products, said hydrophile synthetic products beingcharacterized by the formula V in which R is a hydrocarbon radicalcontaining a phenyl group and not more than? carbon atoms and n and nare whole numbers with the provisothat it plus )1 equals a sum varyingfrom 15 to n is a' whole number not I group consisting of acyclic andisocyclic polycarboxy acids composed of carbon, hydrogen and oxygen ofthe formula R V .7 (CO0H),w a and with the further proviso that theparent dihydroxy compound prior to esterification be water-insoluble andkerosene-soluble. a

4. Hydrophile synthetic products; said hydroph ile synthetic productsbeing characterized by the formula and i1 and'n are whole numbers withthe proviso that n. i

from the group consisting of acyclic and isocyclic poly-' of hydrogenatoms, and the monovalent radical (CsHeOh H in which n'" is a COOH and nand n are whole numbers with the proviso that it plus n equals a sumvarying from 15 to 80; and R is the radical of a dicarboxy acid havingnot more than 14 8 carbon atoms and selected from the group consistingof acyclic and isocyclic dicarboxy acids composed of carbon, hydrogenand oxygen of the formula COOH and with the further proviso that theparent dihydroxy compound prior to esterification be water-insoluble andkerosene-soluble.

6. The products of claim 5 wherein the dicarboxy acid is phthalic acid.

7. The products of claim 5 wherein the dicarboxy acid is maleic acid.

8. The products of claim 5 wherein the dicarboxy acid is oxalic acid.

9. The products of claim 5 wherein the dicarboxy acid is citraconicacid.

10. The products of claim 5 wherein the dicarboxy acid is diglycollicacid.

No references cited.

1.HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTSBEING A COGENERIC MIXTURE SELECTED FROM THE CLASS CONSISTING OF ACIDICFRACTIONAL ESTERS AND ACIDIC AMIDO DERIVATIVES OBTAINED BY REACTIONBETWEEN (A) A POLYCARBOXY ACID OF THE STRUCTURE